WO2019130507A1 - Active material holding tube, active material holding tube group, electrode, and lead storage battery - Google Patents

Abstract

Each active material holding tube 111 comprises a pipe-shaped base material 14 formed by affixing a base material section 14a and a base material section 14b to each other.

Description

Active material holding tube, active material holding tube group, electrode and lead storage battery

The present invention relates to an active material holding tube, an active material holding tube group, an electrode and a lead storage battery.

Lead storage batteries are widely used as industrial or consumer secondary batteries, and in particular, lead storage batteries for electric vehicles (for example, lead storage batteries for automobiles, so-called batteries) or UPS (Uninterruptible Power Supply), disaster prevention (very ) There is a large demand for lead-acid batteries for back-up such as wireless and telephone.

As a lead storage battery, for example, a cylindrical tube, a cored bar (current collector) inserted in the tube, and an electrode material filled between the tube and the cored bar are used. For example, Patent Document 1 below discloses, as a tubular tube, a woven fabric tube mainly composed of glass fiber or synthetic fiber.

JP-A-8-203506

By the way, in order to use lead acid batteries suitably for a long period of time, it is important to achieve excellent cycle characteristics, and it is required to improve the cycle characteristics of lead acid batteries.

An object of the present invention is to provide an active material holding tube, an active material holding tube group and an electrode capable of improving the cycle characteristics of a lead storage battery. Another object of the present invention is to provide a lead-acid battery having excellent cycle characteristics.

The present invention provides, as a first aspect, a tube for holding an active material, comprising a tubular base material formed by one base portion and another base portion adhering to each other.

The inventor has found the following findings. That is, the tube for holding an active material may be manufactured by connecting a plurality of base portions to each other to form a cylindrical base as follows. First, after two sheets of substrates are disposed to face each other, one substrate and another substrate are formed by a plurality of substantially parallel linear connection portions (for example, sutured portions) formed at substantially equal intervals. And connect. Next, the base material is impregnated with the resin component, and then the base material is dried or the like, whereby the active material holding structure has a structure in which a plurality of tubes for holding active material having a cylindrical base material are connected through the connection portion. Tube groups are obtained. When an unnecessary part (for example, a base material part which does not constitute a cylindrical base material) remains at an end of the arrangement direction of the active material holding tubes when forming the active material holding tube group, Unnecessary parts can be cut and removed. In this case, the connection between the substrates in the active material holding tube disposed at the end of the active material holding tube in the direction in which the tubes are arranged is exposed. Here, in the case where the connection portion between the base portions has a space through which the electrode material can pass (for example, the gap of the mesh of the suture portion), or in the active material holding tube during charging and discharging of the lead storage battery. When the connection between the base members is broken due to an increase in the internal pressure of the electrode, etc., the electrode material may leak from the active material holding tube to the electrolyte, and as a result, the cycle characteristics of the lead storage battery deteriorate. .

On the other hand, in the tube for holding an active material according to the first aspect, a space in which the electrode material can pass is a connection between the base portions because one base portion and the other base portion are fixed to each other. Even if it is formed in the part, the space is closed by the fixing part. In addition, since the adhesion between the base portions is excellent, the active material holding tube expands even if the internal pressure in the active material holding tube increases during charge and discharge of the lead storage battery. It is suppressed that the connection part of base-material parts is damaged. Since the leak of the electrode material to electrolyte solution can be suppressed by these, cycle characteristics can be improved.

In the first aspect, one base portion and the other base portion may be fixed to each other by fusion bonding.

According to a second aspect of the present invention, there is provided a tubular base material formed by connecting one base portion and another base portion to each other, and one base portion and one outer side of the tubular base. Providing a tube for holding an active material, comprising: a covering portion contacting a connection portion connecting the other base portions to each other.

In the tube for holding an active material according to the second aspect, the space in which the electrode material can pass is a substrate by the covering portion being in contact with the connection portion connecting the one base portion and the other base portion to each other. Even if it is formed in the connection part of parts, leakage of the electrode material from the space to the outside is suppressed by the covering part. Thereby, since the leakage of the electrode material to the electrolytic solution can be suppressed, the cycle characteristics can be improved.

In a second aspect, the covering may comprise an adhesive.

According to a third aspect of the present invention, there is provided an active material holding tube group including a plurality of active material holding tubes arranged in parallel with one another, wherein the active material holding tube is a plurality of active material holding tubes. The connection portion, which is disposed on at least one of the two end portions of the active material holding tube group in the side-by-side arrangement direction, and which connects one base portion and the other base portion to each other is a plurality of active material holding tubes Provided is a group of tubes for holding an active material, which faces the outside of the group of tubes for holding an active material in the side-by-side direction.

In the active material holding tube group of the third aspect, the connection portion for connecting the one base portion and the other base portion to each other is the active material holding tube group in the direction in which the plurality of active material holding tubes are arranged. Although it faces outward, leakage of the electrode material to the electrolytic solution can be suppressed by using the above-described tube for holding an active material. Thereby, cycle characteristics can be improved.

According to a fourth aspect of the present invention, there is provided an electrode including the above-described active material holding tube group, in which a core metal is disposed inside a cylindrical base material.

In the electrode of the fourth aspect, leakage of the electrode material to the electrolytic solution is suppressed by using the above-described tube group for holding an active material. Thereby, the lead storage battery provided with this electrode can improve cycle characteristics.

According to a fifth aspect of the present invention, there is provided an electrode including an active material holding tube group including a plurality of active material holding tubes juxtaposed to each other, wherein the plurality of active material holding tubes are arranged in parallel. The active material holding tube disposed on at least one of both end portions of the active material holding tube group has a cylindrical base material, and the cylindrical base material is formed by connecting one base portion to another base portion. The core metal is disposed inside the cylindrical base material, and the connection part connecting the one base material part and the other base material part to each other is active in the arranging direction of the plurality of active material holding tubes. An electrode is provided that faces the outside of the substance holding tube group and is covered by a covering.

In the electrode of the fifth aspect, the connection portion connecting the one base portion and the other base portion faces the outside of the active material holding tube group in the direction in which the plurality of active material holding tubes are arranged. However, even if a space through which the electrode material can pass is formed in the connection portion between the base portions by covering the connection portion with the covering portion, the electrode material may leak from the space to the outside. It is suppressed by the covering portion. Thereby, since the leakage of the electrode material to the electrolytic solution can be suppressed, the cycle characteristics can be improved.

The 5th mode may be a mode in which a covering part has a cylindrical part and a core metal is not arranged inside a cylindrical part.

The 5th mode may be a mode where a tubed part is formed by connecting one base portion and another base portion to each other by stitching.

The fifth aspect may be an aspect in which the inner diameter of the tubular portion is smaller than the inner diameter of the tubular base. As a result, the space occupied by the cylindrical portion can be reduced, and it is not necessary to make the electrode excessively large.

The present invention provides, as a sixth aspect, a lead-acid battery comprising the above-described electrode. The lead storage battery of the sixth aspect includes the electrode having the above-described active material holding tube, and therefore, the leakage of the electrode material to the electrolytic solution can be suppressed. Thereby, cycle characteristics can be improved.

According to the present invention, it is possible to provide an active material holding tube, an active material holding tube group and an electrode which can improve the cycle characteristics of a lead storage battery. Furthermore, the present invention can provide a lead storage battery excellent in cycle characteristics.

It is an end elevation showing typically the lead acid battery concerning one embodiment. (A) is a perspective view which shows typically the tube group for active material retention which concerns on one Embodiment, (b) is an enlarged view which shows a part of tube group for active material retention of (a). It is an end elevation showing typically the tube group for active material maintenance concerning other embodiments. It is an end elevation showing typically the tube group for active material maintenance concerning other embodiments.

Hereinafter, embodiments of the present invention will be described with reference to the drawings as appropriate. However, the present invention is not limited to the following embodiments. The sizes of components in the respective drawings are conceptual, and the relative relationship between the sizes of the components is not limited to those shown in the respective drawings.

<Lead storage battery>
First Embodiment
FIG. 1 is an end view schematically showing a lead storage battery according to a first embodiment. FIG. 2 is a perspective view schematically showing an active material holding tube group of the lead storage battery shown in FIG. FIG. 2A is a perspective view schematically showing an active material holding tube group. FIG.2 (b) is an enlarged view which shows a part of tube group for active material holding in the area | region P of Fig.2 (a).

As shown in FIG. 1, the lead storage battery 1 is a lead storage battery including a positive electrode 10, a negative electrode 20, and a separator 30. The positive electrode 10, the negative electrode 20, and the separator 30 are accommodated in a battery case (not shown). The positive electrode 10 and the negative electrode 20 are alternately disposed via the separators 30. The inside of the battery case is filled with the electrolyte solution 40.

The positive electrode 10 has a plate shape, and is, for example, an electrode (positive electrode plate) including a cylindrical electrode group 12 including a plurality of cylindrical electrodes (rod-shaped electrodes) 11 arranged in parallel to one another. The number of cylindrical electrodes 11 is, for example, 2 to 19. Each cylindrical electrode 11 includes a tube for holding an active material (a tube for holding an active material (also referred to as a "gauntlet") 111, a cored bar (current collector) 112 inserted in the tube 111, a tube 111, and a core And the positive electrode material 113 filled in the gold 112. The positive electrode material 113 contains a positive electrode active material after formation, and the tube 111 holds at least an active material (positive electrode active material).

At the bottom end of the battery case in the axial direction (longitudinal direction) of the tube 111 (lower end of the tube 111), a coupling (not shown) for holding the tube 111 and the cored bar 112 is attached There is. Further, the upper end of the battery case in the axial direction of the tube 111 (the opening for inserting the core metal 112 and filling the raw material (lead powder or the like) of the positive electrode material 113) (not shown) ) May be further attached.

As shown in FIG. 2, the tubes 111 of the plurality of cylindrical electrodes 11 arranged in parallel to one another constitute a tube group for holding an active material (a tube group for holding an active material) 13a. That is, the tube group 13a includes a plurality of tubes 111 juxtaposed to one another.

The tube 111 includes a tubular base (a tubular base; a tubular base portion) 14. The cross-sectional shape perpendicular to the axial direction (longitudinal direction) of the cylindrical base material 14 may be a circle, an ellipse, a rounded square, or the like. The length L of the tubular base 14 is, for example, 160 to 400 mm. The outer diameter D _14a of the cylindrical base material 14 is, for example, 5 to 12 mm. The inner diameter D _{14 b} of the cylindrical base 14 is, for example, 5 to 10 mm.

The cylindrical base 14 includes a base portion (one base portion) 14 a and a base portion (other base portion) 14 b. The cylindrical base 14 is formed by connecting the base 14 a and the base 14 b to each other. As shown in FIG. 2 (b), the base portion 14a and the base portion 14b are disposed to face each other, and the base portion 14a constitutes one half of the cylindrical base 14 and the base portion 14 b constitutes the other half of the cylindrical base material 14. The base material part 14a and the base material part 14b may be derived from separate base materials (two base materials) and may be derived from one folded base material. In the tube 111, the base material portion 14a and the base material portion 14b respectively constitute a half circumference of the cylindrical base material 14, but the half circumference of the cylindrical base material 14 may not necessarily be formed.

Materials for forming the base portions 14a and 14b include resins such as polyolefin, polyethylene terephthalate, polystyrene, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), polycarbonate (PC), etc .; Inorganic fiber materials such as fiber, silicon carbide, alumina and the like can be mentioned. The thickness of the base portions 14a and 14b is, for example, 100 to 1000 μm, respectively.

The base portions 14a and 14b are formed of a porous body and have pores. The base portions 14a and 14b may be formed of, for example, a woven or non-woven fabric. The average pore size of the substrate may be, for example, 1 to 50 μm. The average pore diameter can be measured by a pore distribution measuring apparatus (for example, AUTO PORE IV 9520 manufactured by Shimadzu Corporation). The basis weight of the base portions 14a and 14b may be, for example, 100 to 200 g / m ² . The weight per unit area means the mass per unit area measured in accordance with JIS L1913.

In the tube 111, the resin may be held on the cylindrical base material 14. Examples of the resin include acrylic resin, epoxy resin, phenol resin, melamine resin, styrene resin and the like. The resin may be held on the inner surface or the outer surface of the cylindrical base 14 or on the surface in the pores of the cylindrical base 14, and may be attached to the cylindrical base 14. . The resin may be held on a part of the cylindrical base material 14 or may be held on the whole of the cylindrical base material 14.

The end portions of the base portion 14 a and the base portion 14 b are connected to each other via the linear connection portion 15. Connecting portions 15 are arrayed substantially in parallel to each other at a substantially equal interval in the outer diameter D _14a portion of the tubular substrate 14. The shape of the connection portion 15 may be continuous linear, or may be intermittent linear. The connecting portion 15 has a role of connecting the base portion 14a and the base portion 14b, and also has a role of connecting the cylindrical base members 14 arranged parallel to each other. The connection part 15 should just be provided so that the base material part 14a and the base material part 14b may not isolate | separate, for example, the stitch (suture part) by welding, welding (welding), knitting, weaving, adhesion etc. It may be. When the connection portion 15 is formed by a stitch, the stitch may be a stitch by lock stitching, single ring stitching, double ring stitching, flat stitching or the like.

In the tube 111 disposed on at least one of both ends of the tube group 13a in the direction in which the plurality of tubes 111 are juxtaposed, the connecting portion 14c located at the end of the base portion 14a and the base portion 14b is from the connecting portion 15 It projects outwards. The width W of the connection portion 14c in the direction in which the tubes 111 are arranged may be, for example, 0.1 to 11 mm. The length of the connection portion 14 c in the direction (axial direction of the tube 111) orthogonal to the juxtaposed direction of the tubes 111 may be the same as the length L of the tube 111.

The base portion 14a and the base portion 14b are fixedly connected to each other at the connection portion 14c, and are connected to each other by, for example, fusion bonding, adhesion (adhesive agent), welding or the like. That is, the connection portion 14c connecting the base portion 14a and the base portion 14b to each other is a fixed portion (for example, a fusion bonding portion), and the tube 111 is a connection portion 16 connecting the base portion 14a and the base portion 14b to each other. In addition to the connection part 15, it has the connection part 14c. In the connection portion 14c, portions derived from the base portion 14a and the base portion 14b are integrated by adhesion (for example, fusion). The fixing portion may be formed on at least a part of a region where the base portion 14a and the base portion 14b are in contact with each other. For example, the fixing portion may be formed on at least a part of the connecting portion 14c in the axial direction of the tube 111, and the fixing portion may be formed on the entire connecting portion 14c in the axial direction of the tube 111. As a modification of the tube for holding an active material according to the first embodiment, the base 14 a and the base 14 b may be connected to each other only by the connection 14 c without providing the connection 15.

The cored bar 112 is disposed at the center of the tube 111 along the axial direction of the tube 111. The cored bar 112 can be obtained, for example, by casting using a pressure casting method. The constituent material of the core metal 112 may be any conductive material, and examples thereof include lead alloys such as lead-calcium-tin alloys and lead-antimony-arsenic alloys. The lead alloy may contain selenium, silver, bismuth and the like. The cross-sectional shape perpendicular to the axial direction (longitudinal direction) of the core metal 112 may be circular, oval or the like. The length of the cored bar 112 is, for example, 170 to 400 mm. The diameter of the cored bar 112 is, for example, 2.0 to 4.0 mm.

The positive electrode material 113 contains a positive electrode active material after formation, and may further contain an additive as required. The positive electrode material after formation can be obtained, for example, by forming an unformed positive electrode material containing a raw material of the positive electrode active material. The positive electrode material after formation may be obtained by, for example, ripening and drying a positive electrode material paste containing a raw material of the positive electrode active material to obtain an unformed positive electrode material and then forming a non-formed positive electrode material. As a raw material of a positive electrode active material, lead powder, red lead, etc. are mentioned. Examples of the positive electrode active material in the positive electrode material after formation include lead dioxide and the like.

Examples of the additive for the positive electrode material include reinforcing short fibers and the like. As the reinforcing staple fibers, acrylic fibers, polyethylene fibers, polypropylene fibers, polyethylene terephthalate fibers (PET fibers) and the like can be mentioned.

The negative electrode 20 has a plate shape, and is, for example, a paste type negative electrode plate. The negative electrode 20 has a negative electrode current collector and a negative electrode material held by the negative electrode current collector. A plate-like current collector can be used as the negative electrode current collector. The compositions of the negative electrode current collector and the core metal of the positive electrode may be identical to each other or different from each other.

The negative electrode material contains a negative electrode active material after formation, and may further contain an additive as required. The negative electrode material after the formation can be obtained by, for example, maturing and drying the negative electrode material paste containing the raw material of the negative electrode active material to obtain an unformed negative electrode material and then forming the unformed negative electrode material. As a raw material of a negative electrode active material, a lead powder etc. are mentioned. Examples of the negative electrode active material in the negative electrode material after formation include porous sponge lead.

As an additive of the negative electrode material, a resin having at least one selected from the group consisting of barium sulfate, reinforcing short fibers, carbon material (carbonaceous conductive material), sulfone group and sulfonate group (sulfone group and / or sulfone And the like) and the like. As reinforcing short fibers, reinforcing short fibers similar to the positive electrode material can be used.

Examples of carbon materials include carbon black and graphite. Examples of carbon black include furnace black (Ketjen Black (registered trademark) and the like), channel black, acetylene black, thermal black and the like.

Examples of resins having a sulfone group and / or a sulfonate group include lignin sulfonic acid, lignin sulfonic acid salts, and condensates of phenols with aminoaryl sulfonic acid and formaldehyde. Examples of lignin sulfonates include alkali metal salts of lignin sulfonic acid. Examples of phenols include bisphenol-based compounds such as bisphenol. Examples of aminoarylsulfonic acid include aminobenzenesulfonic acid and aminonaphthalenesulfonic acid.

One surface of the separator 30 is in contact with the positive electrode 10, and the other surface of the separator 30 is in contact with the negative electrode 20. Each of the positive electrode 10 and the negative electrode 20 is sandwiched by the separators 30. Each of the positive electrode 10 and the negative electrode 20 may be sandwiched by two separators, and may be sandwiched by one folded separator. An electrolyte solution 40 is filled in a space around the positive electrode 10 between the separators 30 and 30.

The material of the separator is not particularly limited as long as it blocks the electrical connection between the positive electrode and the negative electrode and allows the electrolyte to permeate. The material of the separator may, for example, be a microporous polyethylene; a mixture of glass fibers and a synthetic resin.

The manufacturing method of the lead storage battery concerning a 1st embodiment is explained. The method of manufacturing a lead storage battery according to the first embodiment is, for example, a method of manufacturing a lead storage battery including, as a positive electrode, an electrode having a tube group for holding an active material. The method of manufacturing a lead storage battery according to the first embodiment includes the step of obtaining an electrode by the method of manufacturing an electrode according to the first embodiment. The method of manufacturing an electrode according to the first embodiment includes the step of obtaining a tube for holding an active material by the method of manufacturing a tube for holding an active material according to the first embodiment.

The method of manufacturing a lead storage battery according to the first embodiment includes, for example, an electrode preparation step of obtaining an electrode (positive electrode and negative electrode), and an assembly step of assembling a component including the electrode to obtain a lead storage battery. When the electrode is unformed, the electrode includes, for example, an electrode material (positive electrode material or negative electrode material) containing a raw material of the electrode active material (positive electrode active material or negative electrode active material), and a current collector holding the electrode material (Positive electrode current collector or negative electrode current collector). The electrode after formation includes, for example, an electrode material containing an electrode active material and the like, and a current collector that serves as a conductive path for current from the electrode material and holds the electrode material.

The electrode production process has a positive electrode production process and a negative electrode production process. The positive electrode preparation step includes, for example, a tube preparation step and a finishing step.

In the method of manufacturing a tube for holding an active material in the tube manufacturing process, the base portion 14 a and the base portion 14 b are fixed to each other to form the cylindrical base 14. For example, in the tube manufacturing process, first, two sheet-like base materials are prepared. After the these substrates are opposed each other, substantially regular intervals substantially parallel plurality of linear connecting portions mutually arranged at a (cylindrical outer diameter D _14a minute intervals the substrate 14) ( For example, the base material portion 14a of one base material and the base material portion 14b of another base material are connected by the suture portion 15). And between the adjacent connection parts 15, between base material part 14a and base material part 14b is formed cylindrical, and cylindrical base material 14 is obtained. Thereafter, a tube including the cylindrical base 14 is obtained by obtaining a fixed part connecting the base 14a and the base 14b to each other as the connection 14c located at the end of the base 14a and the base 14b. Get 111 Moreover, thereby, the tube group 13a containing the some tube 111 mutually arranged in parallel is obtained.

When an unnecessary portion (for example, a base portion which does not constitute a cylindrical base material) remains at the end of the direction in which the tubes 111 are arranged in parallel when the tube group 13a is formed, the unnecessary portion is cut It can be removed.

As a method of obtaining the fixed portion as the connection portion 14c located at the end of the base portion 14a and the base portion 14b, the base portion 14a and the base portion 14b are fixed (for example, melted) to form a fixed portion (for example, fusion) The method is not particularly limited as long as it is a method in which the In the case where a fusion-bonded portion is obtained as the fixed portion, for example, unnecessary portions at the end portions in the arrangement direction of the tubes 111 may be melted and removed. Melting may be performed by a method using heat, a laser, ultrasonic waves or the like.

In the case of holding the resin on the cylindrical base material 14, for example, after impregnating the base material with a liquid containing a resin (for example, an emulsion in which the resin is dispersed in water), for example, 1 to 3 at 60 to 130 ° C. It can be dried for hours. The operation for impregnating the liquid containing the resin into the base material may be either before or after the cylindrical portion between the base portion 14a and the base portion 14b is formed.

As a method of forming the cylindrical base member 14 by forming a cylindrical shape between the base portion 14 a and the base portion 14 b between the adjacent connection portions 15, a rod shape is provided between the base portion 14 a and the base portion 14 b. A method of inserting a body and molding; a method of expanding between the base portion 14a and the base portion 14b at the time of drying after impregnating a liquid containing a resin into the base, and the like.

In the finishing step, for example, a positive electrode having a cored bar inserted into a tube and a positive electrode material filled between the tube and the cored bar is obtained. In the finishing step, for example, after supplying the raw material of the positive electrode material and the core metal into the tube, the lower end of the tube is closed to obtain a positive electrode having an unformed positive electrode material. In the finishing step, for example, after supplying a slurry containing a solvent (water, organic solvent, etc.), sulfuric acid, and a raw material of the positive electrode material and a core metal into the tube, the lower end of the tube is closed to form unformed The positive electrode having the positive electrode material of

In the negative electrode preparation step, for example, the negative electrode material paste containing the raw material of the negative electrode active material is filled in a negative electrode current collector (for example, current collector grid (cast grid, expanded grid, etc.)) and then aged and dried. A negative electrode having an unformed negative electrode material can be obtained. Aging can be carried out, for example, in an atmosphere at a temperature of 35 to 85 ° C. and a humidity of 50 to 98 RH% for 15 to 60 hours. Drying can be carried out, for example, at a temperature of 45 to 80 ° C. for 15 to 30 hours.

The negative electrode material paste may further contain, for example, the above-described additive in addition to the raw material of the negative electrode active material. The negative electrode material paste may further contain a solvent and sulfuric acid. As a solvent, water and an organic solvent are mentioned, for example.

In the case of using an additive such as barium sulfate, a carbon material, a reinforcing short fiber, a resin having a sulfone group and / or a sulfonate group in the negative electrode material paste, the compounding amount of barium sulfate is, for example, 100 of the raw material 100 of the negative electrode active material. The amount is 0.01 to 2 parts by mass with respect to the parts by mass. The compounding amount of the carbon material is, for example, 0.1 to 3 parts by mass with respect to 100 parts by mass of the raw material of the negative electrode active material. The blending amount of the reinforcing short fibers is, for example, 0.01 to 0.3 parts by mass with respect to 100 parts by mass of the raw material of the negative electrode active material. The compounding amount of the resin having a sulfone group and / or a sulfonate group is, for example, 0.01 to 2 parts by mass in terms of resin solid content with respect to 100 parts by mass of the raw material of the negative electrode active material.

In the assembly process, for example, an unformed positive electrode and an unformed negative electrode are stacked via a separator, and the current collecting portion of the electrode of the same polarity is welded with a strap to obtain an electrode group. This electrode group is disposed in a battery case to produce an unformed battery. Next, dilute sulfuric acid is added to the unformed battery and direct current is applied to form a battery. The specific gravity of sulfuric acid after formation is adjusted to an appropriate specific gravity to obtain a lead-acid battery. The specific gravity of sulfuric acid (before formation) is, for example, 1.100 to 1.260.

The formation conditions and the specific gravity of sulfuric acid can be adjusted according to the size of the electrode. In addition, the chemical conversion treatment is not limited to being performed after the assembly process, and may be performed in the electrode manufacturing process (tank formation).

In the tube 111 for holding an active material according to the first embodiment, the base material portion 14a and the base material portion 14b are fixed to each other so that the space through which the electrode material can pass is the base material portion 14a and the base material portion 14b. Even if they are formed in the connection portions 16 between each other, the space is blocked by the fixed material (for example, a fusion material). Further, since the adhesion between the base portion 14a and the base portion 14b is excellent in adhesion, even if the internal pressure in the tube 111 is increased during charge and discharge of the lead storage battery 1, the tube 111 expands. Thus, breakage of the connection portion 16 between the base portion 14a and the base portion 14b is suppressed. Since the leak of the electrode material to electrolyte solution can be suppressed by these, cycle characteristics can be improved.

Further, in the first embodiment, the tube 111 has both the connection portion 14 c and the connection portion 15 as the connection portion 16 which connects the base portion 14 a and the base portion 14 b to each other. In this case, since the adhesion between the base portion 14a and the base portion 14b in the connection portion 16 is further excellent, even if the internal pressure in the tube 111 is increased during charge and discharge of the lead storage battery 1, the tube 111 is It is further suppressed that the connection part 16 of base material part 14a and base material part 14b is damaged by expansion. Thereby, since the leakage of the electrode material to the electrolytic solution can be further suppressed, the cycle characteristics can be further improved.

Second Embodiment
A lead storage battery according to a second embodiment will be described. About the structure and part corresponding to the lead storage battery 1 which concerns on 1st Embodiment, the same code | symbol is attached | subjected and the overlapping description is abbreviate | omitted.

FIG. 3 is an end view schematically showing a tube group for holding an active material in a lead storage battery according to a second embodiment. In the second embodiment, the configuration of the tube 111a included in the tube group 13b is different from the tube 111 for holding an active material according to the first embodiment. That is, the tube 111a includes the covering portion 17 in contact with the connection portion 16 of the base portion 14a and the base portion 14b. As shown in FIG. 3, the tube 111 a is formed by connecting the base 14 a and the base 14 b to each other, and the base 14 a at the outer peripheral side of the cylindrical base 14. And a covering portion 17 in contact with the connection portion 16 connecting the base portions 14b to each other. The connection portion 16 of the tube 111a disposed on at least one of the both end portions of the tube group 13b in the direction in which the plurality of tubes 111a are arranged faces the outside of the tube group 13b in the direction in which the plurality of tubes 111a are arranged. The portion 17 is in contact with the connection portion 16. The base portion 14 a and the base portion 14 b in the connection portion 16 are separately disposed without being integrated. In addition, as a modification of the tube for holding an active material according to the second embodiment, the connecting portion 16 in which the base portion 14a and the base portion 14b are in contact with each other is fixed by the covering portion 17 without providing the connecting portion 15. You may

The covering portion 17 may contain an adhesive. Adhesives: acrylic adhesives containing acrylic resin or methacrylic resin; silicone adhesives containing silicone resin; urethane adhesives containing urethane resin; epoxy resins containing epoxy resin; phenol resins containing phenol resin etc. It may be. As the adhesive, a curable adhesive may be used.

The covering portion 17 may be in contact with and cover the connecting portion 16 of the base portion 14a and the base portion 14b, and may be disposed so as to cover the entire periphery of the connecting portion 16 as shown in FIG. . The covering portion 17 may be disposed on at least a part of the axial direction of the tube 111, and may be disposed on the entire axial direction of the tube 111. The covering portion 17 may be interposed between the base portion 14a and the base portion 14b in the connection portion 16 and may be impregnated in the base portion 14a and the base portion 14b.

The manufacturing method of the lead storage battery concerning a 2nd embodiment is explained. The method of manufacturing a lead storage battery according to the second embodiment is, for example, a method of manufacturing a lead storage battery including, as a positive electrode, an electrode having a tube group for holding an active material. The method for producing a lead storage battery according to the second embodiment includes the step of obtaining an electrode by the method for producing an electrode according to the second embodiment. The method of manufacturing an electrode according to the second embodiment includes the step of obtaining a tube for holding an active material by the method of manufacturing a tube for holding an active material according to the second embodiment.

The lead storage battery according to the second embodiment is, for example, an electrode manufacturing process for obtaining an electrode (a positive electrode and a negative electrode) and a component member including the electrode, as in the method for manufacturing a lead storage battery according to the first embodiment. And an assembly process to obtain The assembly process may be the same method as in the first embodiment. The negative electrode preparation step in the electrode preparation step may be the same step as the first embodiment. The finishing process in the positive electrode production process may be the same process as the first embodiment.

In the method of manufacturing a tube for holding an active material in the tube manufacturing step of the second embodiment, the coating in contact with the connection portion 16 connecting the base portion 14a and the base portion 14b to each other on the outer peripheral side of the cylindrical base 14 The portion 17 is formed. For example, after the base portion 14a of one base material and the base portion 14b of another base material are connected by the connection portion (for example, suture portion) 15 to obtain the connection portion 16, the base portion 14a and the base material A covering portion 17 is formed in contact with the connection portion 16 of the portion 14b. When an adhesive is used as the covering portion 17, the covering portion 17 can be obtained by applying the adhesive to the connection portion 16. The adhesive may be cured after the adhesive is applied to the connection 16.

In the tube 111a for holding an active material according to the second embodiment, the space where the electrode material can pass by the covering portion 17 being in contact with the connection portion 16 connecting the base portion 14a and the base portion 14b to each other. Is formed on the connection portion 16 between the base portion 14a and the base portion 14b, leakage of the electrode material from the space to the outside is suppressed by the covering portion 17. Thereby, since the leakage of the electrode material to the electrolytic solution can be suppressed, the cycle characteristics can be improved.

In the second embodiment, the covering portion 17 is disposed to cover the entire periphery of the connection portion 16. Thereby, since the leakage of the electrode material to the electrolytic solution can be further suppressed, the cycle characteristics can be further improved.

Third Embodiment
A lead storage battery according to a third embodiment will be described. About the structure and part corresponding to the lead storage battery 1 which concerns on 1st Embodiment, the same code | symbol is attached | subjected and the overlapping description is abbreviate | omitted.

FIG. 4 is an end view schematically showing a tube group for holding an active material in a lead storage battery according to a third embodiment. In the third embodiment, the configuration of the tube 111b included in the tube group 13c is different from the tube 111 for holding an active material according to the first embodiment. That is, in the tube 111b disposed on at least one of the both ends of the tube group 13c in the direction in which the plurality of tubes 111b are juxtaposed, as shown in FIG. 4, the connection portion connecting the base portion 14a and the base portion 14b to each other A portion 16 faces the outside of the tube group 13c in the direction in which the plurality of tubes 111b are arranged, and is covered by the covering portion 18.

As shown in FIG. 4, the covering portion 18 has a cylindrical portion 19. The cylindrical portion 19 has, for example, a bag shape. The cylindrical portion 19 is formed by connecting the base portion (one base portion) 19a and the base portion (other base portion) 19b to each other, and the base portion 19a and the base portion 19b are formed. And a connection portion 19c connecting the base portion 19a and the base portion 19b to each other. The base portion 19 a and the base portion 19 b are disposed to face each other, the base portion 19 a constitutes one half of the cylindrical portion 19, and the base 19 b is the other half of the cylindrical portion 19. Are configured. In the cylindrical part 19, although the base material part 19a and the base material part 19b each comprise half of the circumference of the cylindrical part 19, it is not necessary to necessarily form half circumference of the cylindrical part 19.

The base 19a and the base 19b may be formed of the same material as the cylindrical base 14 of the tube 111b, and may be formed of different materials. The base 19a and the base 19b may be integral with the cylindrical base 14 of the tube 111b, or may be separate from the cylindrical base 14. That is, the covering portion 18 may be a part of a member continuous with the cylindrical base 14, or may be a member different from the cylindrical base 14.

The cylindrical portion 19 extends, for example, along the longitudinal direction of the cylindrical base 14 of the tube 111b. That is, the cylindrical portion 19 is juxtaposed to the tube 111b along the direction in which the plurality of tubes 111b are arranged. The connection portion 16 of the cylindrical base 14 of the tube 111b disposed on at least one of the both end portions of the tube group 13c in the direction in which the plurality of tubes 111b are juxtaposed is the inner surface of the cylindrical portion 19 (in FIG. Is coated on the inner surface in a state of facing the inner surface).

In FIG. 4, for example, the base portion 19a and the base portion 19b are connected to each other by stitching, and the connection portion 19c is formed. The connection portion 19c is disposed on the opposite side of the tubes 111b in the direction in which the plurality of tubes 111b are juxtaposed. The connection part 19c may be any material such as a sewn part, a fusion part, or an adhesive as long as the base part 19a and the base part 19b are connected to each other. The configuration described above in the first embodiment can be used as the suture portion and / or the fusion portion. As the adhesive, the configuration described above in the second embodiment can be used.

The inner diameter _{D 19} of the cylindrical portion 19, 1.0 mm or more, may be at 2.0mm or more or 4.0mm or more. The inner diameter _{D 19} of the cylindrical portion 19, 11.0 mm or less, may be at 5.0mm or less, or 1.0mm or less. The inside diameter D ₁₉ of the cylindrical portion 19 is, for example, the maximum inside diameter of the cylindrical portion 19. The inner diameter D ₁₉ of the cylindrical portion 19 may be smaller than the inner diameter D _{14 b} of the cylindrical base 14.

In the third embodiment, the core metal is disposed inside the tubular base 14 of the tube 111 b disposed at at least one of the both ends of the tube group 13 c in the direction in which the plurality of tubes 111 b are juxtaposed. An electrode material is filled between the core and the core metal. For example, as in the configuration of FIG. 1, the core metal and the electrode material are disposed in the cylindrical base material 14 in all the tubes 111 b of the tube group 13 c. On the other hand, the core metal and the electrode material are not disposed inside the cylindrical portion 19.

The manufacturing method of the lead storage battery concerning a 3rd embodiment is explained. The method of manufacturing a lead storage battery according to the third embodiment is, for example, a method of manufacturing a lead storage battery including an electrode having an active material holding tube group as a positive electrode. The method of manufacturing a lead storage battery according to the third embodiment includes the step of obtaining an electrode by the method of manufacturing an electrode according to the third embodiment. The method of manufacturing an electrode according to the third embodiment includes the step of obtaining a tube for holding an active material by the method of manufacturing a tube for holding an active material according to the third embodiment.

The lead storage battery according to the third embodiment is, for example, an electrode manufacturing process for obtaining an electrode (a positive electrode and a negative electrode) and a component member including the electrode assembled as in the method for manufacturing a lead storage battery according to the first embodiment. And an assembly process to obtain The assembly process may be the same method as in the first embodiment. The negative electrode preparation step in the electrode preparation step may be the same step as the first embodiment. The finishing process in the positive electrode production process may be the same process as the first embodiment. In the finishing step, the cored bar is not disposed in the cylindrical portion 19.

In the method of manufacturing a tube for holding an active material in the tube manufacturing step of the third embodiment, the cylindrical base material 14 in the tube 111b disposed at least one of the both end portions of the tube group 13c in the juxtaposed direction of the plurality of tubes 111b. Forming the covering portion 17 covering the connection portion 16 in a state where the connection portion 16 connecting the base portion 14a and the base portion 14b to each other faces the outside of the tube group 13c in the direction in which the plurality of tubes 111b are juxtaposed Do. For example, as the base material portion that does not constitute the tubular base material 14, one of the connection portions (for example, the suture portion) 16 may be provided such that the base material portion 19 a and the base material portion 19 b remain at the end of the tube 111 in the arrangement direction. After connecting the base portion 14a of the base and the base portion 14b of the other base, the base portion 19a and the base portion 19b are connected to each other to form the cylindrical portion 19. The connection method of the base 19a and the base 19b may be any of suturing, fusion bonding, placement of an adhesive, and the like.

In the tube 111b for holding an active material according to the third embodiment, the connection portion 16 connecting the base portion 14a and the base portion 14b to each other faces the outside of the tube group 13c in the direction in which the plurality of tubes 111b are arranged. However, even if a space through which the electrode material can pass is formed in the connection portion 16 between the base portion 14a and the base portion 14b by the connection portion 16 being covered with the covering portion 18, from the space Leakage of the electrode material to the outside is suppressed by the covering portion 18. Thereby, since the leakage of the electrode material to the electrolytic solution can be suppressed, the cycle characteristics can be improved.

Further, in the third embodiment, the covering portion 18 has the cylindrical portion 19. In this case, even if the electrode material leaks from the connection portion 16, the leaked electrode material is captured in the cylindrical portion 19, and the leakage of the electrode material to the electrolytic solution is further suppressed. Furthermore, in the third embodiment, the internal pressure inside the cylindrical portion 19 is less likely to rise than the tube 111b filled with the electrode material, so the cylindrical portion 19 expands and the connecting portion 19c is less likely to be damaged. Leakage of the electrode material to the electrolytic solution is further suppressed. These can further improve cycle characteristics.

Furthermore, in the third embodiment, the inner diameter D ₁₉ of the cylindrical portion ₁₉ is smaller than the inner diameter D _{14 b} of the cylindrical base 14. In this case, since the space occupied by the cylindrical portion 19 can be reduced, it is not necessary to make the electrode excessively large.

<Electric car>
Each of the lead storage batteries described above can be used in an electric car. The electric vehicle according to the present embodiment includes the above-described lead storage battery. The method of manufacturing an electric vehicle according to the present embodiment includes the step of obtaining a lead storage battery by the above-described method of manufacturing a lead storage battery. The method of manufacturing an electric vehicle according to the present embodiment includes, for example, a step of obtaining a lead-acid battery by the above-described method of manufacturing a lead-acid battery, and a step of assembling components including the lead-acid battery to obtain an electric vehicle. As an electric car, a forklift, a golf cart, etc. are mentioned. According to the present embodiment, an active material holding tube, an active material holding tube group, an electrode and a lead storage battery used for an electric vehicle are provided. For example, an active material holding tube used for a forklift, an active material holding tube A group, an electrode and a lead-acid battery are provided.

DESCRIPTION OF SYMBOLS 1 ... Lead storage battery, 10 ... Positive electrode (electrode), 13a, 13b, 13c ... Tube group (tube group for active material holding), 14 ... Tubular base material, 14a ... Base material part (one base material part), 14b ... base material part (other base material part), 16 ... connection part, 17, 18 ... coating part, 19 ... cylindrical part, 111, 111a, 111b ... tube (tube for holding active material), 112 ... core metal .

Claims (11)

A tube for holding an active material, comprising a tubular base formed by bonding one base portion and another base portion to each other. The active material holding tube according to claim 1, wherein the one base portion and the other base portion adhere to each other by fusion bonding. A tubular base formed by connecting one base portion and another base portion to each other;
A tube for holding an active material, comprising: a covering part that contacts a connection part that connects the one base material part and the other base material part on the outer peripheral side of the cylindrical base material. The active material holding tube according to claim 3, wherein the covering portion contains an adhesive. An active material holding tube group including a plurality of active material holding tubes arranged in parallel with one another,
The active material holding tube according to any one of claims 1 to 4 is disposed on at least one of both end portions of the active material holding tube group in a direction in which the plurality of active material holding tubes are arranged. Yes,
An active material, wherein a connection portion connecting the one base portion and the other base portion faces the outside of the active material holding tube group in the direction in which the plurality of active material holding tubes are arranged. Holding tube group. A tube for holding an active material according to claim 5 is provided.
An electrode, wherein a core metal is disposed inside the tubular base material. An electrode comprising an active material holding tube group including a plurality of active material holding tubes arranged in parallel with one another,
The active material holding tube disposed on at least one of both end portions of the active material holding tube group in the direction in which the plurality of active material holding tubes are arranged has a cylindrical base material,
The tubular base material is formed by connecting one base part and another base part to each other,
A cored bar is disposed inside the tubular base material,
The connection portion connecting the one base portion and the other base portion to each other faces the outside of the active material holding tube group in the direction in which the plurality of active material holding tubes are arranged, and the covering portion Covered by an electrode. The covering portion has a tubular portion,
The electrode according to claim 7, wherein a cored bar is not disposed inside the cylindrical portion. The electrode according to claim 8, wherein the tubular portion is formed by connecting one base portion and another base portion to each other by stitching. The electrode according to claim 8 or 9, wherein the inner diameter of the cylindrical portion is smaller than the inner diameter of the cylindrical base. A lead-acid battery comprising the electrode according to any one of claims 6 to 10.

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